Electrode material and electrode for III-V group compound semiconductor

ABSTRACT

The invention provides an electrode material having the low contact resistance against a III-V group compound semiconductor, thereby realizing a light emitting device having a high luminance and driven at low voltages. The electrode material of the invention is applied to a III-V group compound semiconductor, which is expressed as a general formula of In x Ga y Al z N, where x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1, and doped with p-type impurities. The electrode material comprises an alloy of Au and at least one metal selected from the group consisting of Mg and Zn.

This application is a continuation of application Ser. No. 08/392,244,filed on Feb. 22, 1995, now U.S. Pat. No. 5,708,301, the entire contentsof which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to an electrode material and an electrodefor a III-V group compound semiconductor.

2. Description of the Related Art

III-V group compound semiconductors expressed as a general formula ofIn_(x)Ga_(y)Al_(z)N, where x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1 are appliedto light emitting device ultra-violet or blue light emitting diodes andultra-violet or blue laser diodes. Properties of these compoundsemiconductors have, however, hardly been elucidated, and no electrodematerials having low contact resistance against the p-type III-V groupcompound semiconductors have been obtained yet.

Development of electrode materials having low contact resistance againstthe p-type III-V group compound semiconductors is highly demanded inorder to realize light emitting devices of favorable electricproperties.

DETAILED DESCRIPTION OF THE INVENTION

One object of the invention is thus to provide an electrode materialhaving the low contact resistance against a III-V group compoundsemiconductor, which is expressed as a general formula ofIn_(x)Ga_(y)Al_(z)N, where x+y+z=1, 0≦x≦1, 0≦y≦1 and 0≦z≦1, and dopedwith p-type impurities.

Another object of the invention is to realize a light emitting devicehaving a high luminance and driven at low voltages.

As a result of extensive studies, the inventors have found that an alloyof Au and a specific metal has a sufficiently low contact resistanceagainst the III-V group compound semiconductors.

The invention is directed to an electrode material applied to a III-Vgroup compound semiconductor, which is expressed as a general formula ofIn_(x)Ga_(y)Al_(z)N, where x+y+z=1, 0≦x≦1, 0≦y≦1 and 0≦z≦1, and dopedwith p-type impurities, the electrode material comprising an alloy of Auand at least one metal selected from a group consisting of Mg and Zn.

Also the invention is directed to an electrode applied to a III-V groupcompound semiconductor, which is expressed as a general formula ofIn_(x)Ga_(y)Al_(z)N, where x+y+z=1, 0≦x≦1, 0≦y≦1 and 0≦z≦1, and dopedwith p-type impurities, the electrode formed with the afformentionedmaterial.

The electrode material of the invention is applicable to III-V groupcompound semiconductors which are expressed as a general formula ofIn_(x)Ga_(y)Al_(z)N, where x+y+z=1, 0≦x≦1, 0≦y≦1 and 0≦z≦1, and dopedwith p-type impurities.

Such III-V group compound semiconductors are prepared, for example, bymolecular beam epitaxy (hereinafter referred to as MBE), byorganometallic vapor phase epitaxy (hereinafter referred to as MOVPE),or hydride vapor phase epitaxy (hereinafter referred to as HVPE). Gassource molecular beam epitaxy (hereinafter referred to as GSMBE) isgenerally applied among the MBE processes, where nitrogen gas, ammoniagas, or another gaseous nitrogen compound is supplied as nitrogensource. The nitrogen source may be chemically inactive, which preventsnitrogen atoms from being easily taken into the crystal. Under suchconditions, the nitrogen source may be excited and activated by amethod, for example microwave excitation, thereby enhancing the intakeefficiency of nitrogen atoms.

In the case of MOVPE, using so called 2 step-growth method, where abuffer layer such as thin film of AlN or GaN is grown on the substrateand the compound semiconductor is grown on the buffer layer, iseffective to obtain the compound semiconductor of good crystallinity(Applied Physics Letters, vol. 48 (1986), p 353, Japanese Journal ofApplied Physics, vol. 30 (1991), p L1705).

Examples of the p-type impurities applicable to the invention includeMg, Zn, Cd, Be, Ca, and Hg. Preferable impurity atoms are Mg and Zn, andmore specifically Mg.

The p-type impurities are given from the materials described below.

As long as a simple body of dopant is controlled to a vapor pressurewhich does not interfere with other molecular beams in a device ofmanufacturing the III-V group compound semiconductor by the process ofGSMBE, the simple body of dopant is directly applied as the p-typeimpurity.

Volatile materials given below may be applied in the process of MOVPE.

Examples of material for giving zinc atoms (Zn) include alkylzincsexpressed as a general formula of R₁R₂Zn, where R₁ and R₂ are,independently from each other, alkyl groups having 1 to 4 carbon atoms,such as dimethylzinc (CH₃)₂Zn and diethylzinc (C₂H₅)₂Zn.

Examples of material for giving magnesium atoms (Mg) includebis(cyclopentadienyl)magnesium (C₅H₅)₂Mg (hereinafter referred to asCp₂Mg), bis(methylcyclopentadienyl)magnesium (CH₃C₅H₄)₂Mg, andbis(isopropylcyclopentadienyl)magnesium (i-C₃H₇C₅H₄)₂Mg.

Examples of material for giving cadmium atoms (Cd) include alkylcadmiumsexpressed as a general formula of R₁R₂Cd, where R₁ and R₂ are,independently from each other, alkyl groups having 1 to 4 carbon atoms,such as dimethylcadmium (CH₃)₂Cd.

Examples of material for giving beryllium atoms (Be) includediethylberyllium (C₂H₅)₂Be and bis(methylcyclopentadienyl)beryllium(CH₃C₅H₄)₂Be.

Examples of material for giving mercury atoms (Hg) includealkylmercuries expressed as a general formula of R₁R₂Hg, where R₁ and R₂are, independently from each other, alkyl groups having 1 to 4 carbonatoms, such as dimethylmercury (CH₃)₂Hg and diethylmercury (C₂H₅)₂Hg.

The electrode material of the invention applied to III-V group compoundsemiconductors is an alloy of Au and at least one metal selected fromthe group consisting of Mg and Zn. Concrete examples are Au—Mg, Au—Znand Au—Zn—Mg alloys.

Preferable concentration range of Mg in the electrode material is 0.1 to2.5% by weight. Preferable concentration range of Zn in the electrodematerial is 1 to 30% by weight.

The electrode material of the invention has the low contact resistanceagainst the III-V group compound semiconductor, thereby realizing alight emitting device having a high luminance and driven at lowvoltages.

The electrode material applicable for the III-V group compoundsemiconductor is prepared in the following manner.

At a first step, a III-V group compound semiconductor, which isexpressed as a general formula of In_(x)Ga_(y)Al_(z)N, where x+y+z=1,0≦x≦1, 0≦y≦1 and 0≦z≦1, and doped with p-type impurities is grownaccording to a known method. The electrode material of the invention isthen vacuum-deposited onto the compound semiconductor. It is preferableto vacuum-deposit the electrode material of the invention after theIII-V group compound semiconductor is irradiated with electron beams orheated to 500° C. or higher temperatures for annealing.

Any known method is applicable to vacuum deposition. For example, anAu—Zn alloy is vacuum-deposited on the compound semiconductor with atungsten boat by the resistance heating process.

In another application, a semiconductor laminate formed by vacuumdeposited Au and a specific metal on the compound semiconductor isannealed to form an alloy on the semiconductor.

In some cases, annealing improves the electric contact.

An atmosphere applied for annealing may be sufficiently purifiednitrogen gas or inert gas such as argon. The temperature of annealing ispreferably in a range of 200° C. to 1,000° C. or more specifically in arange of 300° C. to 900° C. The lower annealing temperature results ininsufficient effects whereas the higher annealing temperature causesdenaturation of constituents of the semiconductor device so as todeteriorate the properties of the semiconductor device.

The time period for annealing is determined according to the annealingtemperature, but is preferably in a range of 1 second to 2 hours or morespecifically in a range of 2 seconds to 30 minutes. The shorterannealing time results in insufficient effects whereas the longerannealing time causes denaturation of constituents of the semiconductordevice so as to deteriorate the properties of the semiconductor deviceor worsen the productivity.

Another metal may further be laid over the electrode which is in contactwith the III-V group compound semiconductor. This enhances themechanical strength and other mechanical properties without damaging theelectric properties.

A concrete example of an electrode, which has the above mentionedlaminate structure, is schematically shown in FIG. 1, where the secondmetal electrode 3 is deposited onto both surfaces of the electrode ofthe invention 2 and of the compound semiconductor 1. The examples of themetals which may be used as the second electrode are, Al, Ti and Cr.Among these metals, Al may be preferably used because of its goodadhesion properties to the compound semiconductor.

In general, an electric contact is made to the second electrode.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows structure of a laminate of electrodes of III-V groupcompound semiconductor where the invention is used as the firstelectrode;

FIG. 2 shows structure of a III-V group compound semiconductor preparedin Example 1;

FIG. 3 shows distinction between a vapor deposited portion and anon-vapor deposited portion on an electrode;

FIG. 4 is a graph showing relationship between annealing temperature ofelectrodes and the forward current in Example 1.

FIG. 5 is a graph showing the depth profile of Au, Mg and Ga in theelectrode of the invention, (a) is for the electrode before the anneal,and (b) for after the anneal.

FIG. 6 is a graph showing relationship between annealing temperature ofelectrodes and the forward current in Example 2.

FIG. 7 is a graph showing relationship between annealing temperature ofelectrodes and the forward current in Example 3.

FIG. 8 is a graph showing relationship between annealing temperature ofthe electrodes and the forward current in Example 4.

EXAMPLES

Preferred examples according to the invention are described in detailalthough the invention is not limited to these examples in any sense.The evaluation of the electrodes was made by comparing thecharacteristics with those of Au electrode, which is made on each p-typeGaN sample used in an example.

Example 1 & Reference 1

A gallium nitride semiconductor was prepared by the process ofatmospheric pressure MOVPE. The gases used here were NH₃, carrier gasH₂, trimethylgallium Ga(CH₃)₃ (hereinafter referred to as TMG). Cp₂Mgwas used as a p-type Mg dopant.

A III-V group compound semiconductor having structure shown in FIG. 2was prepared in the following manner.

A substrate 4 of sapphire single crystal having a C face cleaned withorganic solvent was set on a graphite susceptor installed in a MOVPEreactor. Then the substrate was heated to 1,100° C. in a hydrogen flow.Then the reactor, the susceptor, and the substrate were etched byfurther supply of hydrogen chloride gas at this temperature. The flowrate of hydrogen and hydrogen chloride during the etching was 2 slm and10 sccm for hydrogen and hydrogen chloride respectively. Here, slm andsccm are units of gas flow, where 1 slm is a flow of gas, which occupies1 liter at the normal state, in a minute, and seem is defined as 1000sccm=1 slm. After stopping the supply of hydrogen chloride gas, thesubstrate was further kept at this temperature for 5 minutes. Then abuffer layer 5 of 500 Å thick GaN was grown on the substrate at 600° C.,and then 3 μm thick Mg doped GaN 6 was grown on the buffer layer at1100° C. The amounts of materials supplied during the buffer layergrowth were 2 slm, 2 slm, and 6.7×10⁻⁶ mol/min for H₂, NH₃, and TMG,respectively, and during the growth of Mg doped GaN, 4 slm, 4 slm and4.5×10⁻⁵ mol/min for H₂, NH₃, and TMG, respectively. During the growthof Mg doped GaN layer, H₂ of 100 scem was introduced to the reactorthrough the Cp₂Mg container kept at 30° C. After the growth, thesubstrate was detached from the reactor, and was annealed at 800° C. inthe atmosphere of nitrogen for 20 minutes. A p-type gallium nitridesemiconductor having concentration of carrier of about 2×10¹⁸/cm³ wasprepared accordingly.

Mg and Au were vacuum deposited in this order onto the p-type GaN thusprepared with the pattern shown in FIG. 3. Two samples with differentthickness of deposited metals were prepared, where Mg contents to thetotal amount of the deposited metals were 0.3 and 1% by weight in eachelectrode, with the total thickness of Mg and Au being 1500 Å for eachsample. As a reference sample, Au electrode of 1500 Å thickness was alsodeposited onto the p-type GaN used for the example.

When the inner circular electrode in FIG. 3 is positively biased, thecircuit is forward-biased.

The relationship between the current at a forward bias of 4 V and theannealing temperature of the electrodes are shown in FIG. 4 togetherwith the results of the Au electrode. The samples were annealed in anitrogen atmosphere for 90 seconds. The graph shows that the electrodeof 0.3% Mg concentration by weight annealed at 900° C., and that of 1%Mg concentration by weight annealed at 800° C. or higher temperatureshave better electric contact than the Au electrode.

FIG. 5 shows the depth profile of Au, Mg, and Ga in the electrode of theinvention prepared by the method described in this example, where thetotal thickness of Mg and Au was 1500 Å and the weight of Mg in theelectrode was 1% of the total weight of Au and Mg. The profile wasmeasured by X-ray photoelectron spectroscopy. FIGS. 5(a) and (b)correspond to samples before and after anneal of the electrode,respectively, where the electrode was annealed in a nitrogen atmosphereat 800° C. for 90 seconds. The abscissa of the figure is sputtering timeof the electrode by Ar ion, which corresponds to the depth from thesurface of the electrode. From this figure, it is clear that there areMg layer and Au layer on GaN in this order before the anneal, and thatMg layer is almost disappeared after the anneal, showing that Mgdiffused into the Au layer by making alloy with Au.

Example 2 & Reference 2

AuZn (containing 5% by weight of Zn) electrode having a pattern shown inFIG. 2 as well as an Au electrode (Reference 2) were vacuum deposited inthe depth of 1500-Å onto the p-type gallium nitride semiconductorprepared in the same manner as Example 1. The same relationship as FIG.4 for these samples are shown in FIG. 6. This graph shows that theelectrode of Example 2 has the lower contact resistance against thep-type GaN than the Au electrode when annealed at 400° C. or highertemperatures.

Example 3 & Reference 3

AuZn electrodes of Zn concentration of 1 and 10% by weight with totalthickness of 1,500 Å were prepared in the same manner as Example 1except that Zn was used instead of Mg. An Au electrode of 1,500 Å wasprepared onto the same p-type GaN as a reference (Reference 3). The samererationship with FIG. 4 for these electrodes are shown in FIG. 7. Thegraph shows that the electrodes of Zn concentrations between 1 and 10%by weight have better electric contact compared to Au electrode whenannealed at 400° C. or higher temperatures.

Example 4 & Reference 4

Mg, Zn and Au were deposited in this order onto the p-type GaN preparedin the same manner as Example 1. The total thickness was 1,500 Å, and Mgand Zn concentrations were both 1% by weight. An Au electrode of 1,500 Åwas prepared onto the same p-type GaN as a reference (Reference 4). Thesame relationship with FIG. 4 for these electrodes are shown in FIG. 8.The graph shows that the electrode of Example 4 has better electriccontact compared to Au electrode when annealed at 300° C. or highertemperatures.

What is claimed is:
 1. An electrode material applied to a III-V groupcompound semiconductor expressed as a general formula ofIn_(x)Ga_(y)Al_(z)N, where x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1, saidcompound semiconductor being doped with p-type impurities, saidelectrode material comprising an alloy of Au and at least one metalselected from the group consisting of Mg and Zn, wherein Mg is presentin a concentration range of from 0.1 to 2.5% by weight based on theelectrode material and Zn is present in a concentration range of from 1to 30% by weight based on the electrode material.
 2. An electrodeapplied to a III-V group compound semiconductor expressed as a generalformula of In_(x)Ga_(y)Al_(z)N, where x+y+z=1, 0≦x≦1, 0≦y≦1, and 0≦z≦1,said compound semiconductor being doped with p-type impurities, and saidelectrode being made of the electrode material claimed in claim 1.